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Marine Nitrogen Cycle. Matthieu Heine. Marine Nitrogen Cycle. Global patterns of marine nitrogen fixation and denitrification . Nicolas Gruber and Jorge L. Sarmiento (1997)
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Marine Nitrogen Cycle Matthieu Heine
Marine Nitrogen Cycle • Global patterns of marine nitrogen fixation and denitrification. Nicolas Gruber and Jorge L. Sarmiento (1997) • The oceanic fixed nitrogen and nitrous oxide budgets: Moving targets as we enter the anthropocene?L.A. Codispoti, Jay A. Brandes, J.P. Christensen, A.H. Devol, S.W.A. Naqvi, Hans W. PaerlsandT. Yoshinari (2001)
Schedule • General overview of the marine nitrogen cycle. • Review “Global patterns of marine nitrogen etc”. • Review “The oceanic fixed nitrogen etc”. • Overall conclusion.
Overview N-cycle • Nitrification; Step 1 Ammonia oxidation: NH3 + 1½ O2 → NO2- + H+ + H2O Step 2 Nitrite oxidation: NO2- + 1½ O2 → NO3- • Denitrification; NO3- + 6H+ + 5e-→ ½N2 + 3H2O • Nitrogen fixation; N2 + 8H+ + 8e- + 16ATP --> 2NH3 + H2 + 16ADP + 16Pi (biological) • Assimilation; NO3- preferred • Production/reduction of N20 Depends on circumstances ([O2], [NO2], etc)
“Global patterns of marine nitrogen fixation and denitrification.” • Introduction • The concept of N* • Data considerations • Global observations • Global marine N-budget
Introduction • Uncertainties estimating marine N-budget • Ocean system: Steady State/Dynamic? • Differences in residence times • Data of small spatial and temporal scale • New method in town! N* = N – rn:p P + constant
Concept of N* • Effects on biogeochemical cycles; • Nitrification Jnitr(N) • Denitrification J denitr(N) • N-fixation of N-rich O.M. by diazotrophic organisms J N-rich nitr(N) • Formulas • Γ(N) = Jnitr(N) + J denitr(N) + J N-rich nitr(N) (1) • Γ(P) = Jnitr(P) + J denitr(P) + J N-rich nitr(P) (2) - Γ(Tracer) = dT/dt + u + dT – d * (D-dT) (3)
Concept of N* • Substitution of (1), (2) in (3) • Values of Stoichiometric ratios rN:P nitr. = 16 (Redfield et al.) rN:Pdenitr. = -108,8 (Takahashi et al.) rN:P n-rich nitr. = 125 (Karl et al.)
Concept of N* • Final definition N*; N* = (N-16P + 2,90 μmol kg-1) * 0,87 (4) Γ(N*) = J denitr(N) + 0,76 J N-rich nitr(N) (5)
Absolute value of N* is arbitrary! Only deviation is from the solid line is important; Redfield ratio (16) → deviation is 0. Left-hand side: net effect of N2-fixation (excess P). Right-hand side: net effect of denitrification. Concept of N*
Data Consideration • Sampling in: Atlantic, Pacific and Indian Ocean. • Data used from the GEOSECS, TTO NAS, TTO TAS, SAVE, Atlantis 109 and AJAX-cruises. • Data has been consistent over a longer period of time.
Global marine N-budget • Conclusions; • N-budget from previous literature needs to be adjusted → more N-fixation than expected (especially in the Atlantic); • Not in compliance with other studies that the ocean as a whole is losing fixed nitrogen.
Marine Nitrogen Cycle • Global patterns of marine nitrogen fixation and denitrification. Nicolas Gruber and Jorge L. Sarmiento (1997) • The oceanic fixed nitrogen and nitrous oxide budgets: Moving targets as we enter the anthropocene?L.A. Codispoti, Jay A. Brandes, J.P. Christensen, A.H. Devol, S.W.A. Naqvi, Hans W. PaerlsandT. Yoshinari (2001)
“The oceanic fixed nitrogen and nitrous oxide budgets:Moving targets as we enter the anthropocene?” • Excluded reactions N-cycle • Excluded interactions N-cycle • Dynamics • Conclusion
Excluded reactions N-cycle • Labile components: • NO; • Hydroxylamine (NH2OH). • Bacteria: • Transport NO3- to sulphide-rich sediments; • Denitrification linked to oxidation by HS-; • Excess N2 production.
Excluded interactions N-cycle • Dependence on O2 concentration: • High [O2] → Low N-fixation due to polluted enzyme system; • High [O2] → Low denitrification; • Low [O2] → High N2O production with nitrification. • Interactions with Iron: • Fe/NO3- ratio with N-fixation is ± 60:1. • Oxygen Minimum Zone (OMZ) → High denitrification → high N-fixation → High Fex requirements → Ocean becomes Iron-depleted; • Iron limitation constrains N-fixation thus primary production; • Increase in CO2 in the atmosphere.
Excluded interactions N-cycle • Different C/N ratios; - Less carbon necessary for denitrification than for N-fixation.
Dynamics • Ocean fixed nitrogen sink: Heavily dominated by denitrification. • Ocean fixed nitrogen source: - N-fixation is largest biological source; • Large effect input from rivers.
Conclusion • Difference in fixed nitrogen budgets last long enough to have an significant impact on the CO2 concentrations in the atmosphere. • New calculations; 15-40% more N2 produced than nitrate. • Still excess in N2. • Possible sources of excess N2: • Sedimentary denitrification; • Bacteria oxidise HS- with NO3- producing NH3+. Which under suboxic conditions use Mn to reduce to N2.
Overall conclusion • Balance in marine N-budget; • Existing estimates of water column denitrification are too low; • Underestimated sources: • Anthropogenic sources; and • Input through groundwater.